research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 11| November 2014| Pages 410-414
doi:10.1107/S1600536814023149

Crystal structures of 3,6-di­allyl­tetra­cyclo[6.3.0.04,11.05,9]undeca-2,7-dione and 1,7-di­allyl­penta­cyclo­[5.4.0.02,6. 03,10.05,9]undecane-8,11-dione: allyl­ated caged compounds

Sambasivarao Kotha,a* Vital Seema,a Deepak Deodhara and Mobin Shaikha

aDepartment of Chemistry, Indian Institute of Technology–Bombay, Powai, Mumbai 400 076, India
*Correspondence e-mail: srk@chem.iitb.ac.in

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 14 October 2014; accepted 21 October 2014; online 24 October 2014)

The title compounds, C17H20O2 (1) and C17H18O2 (2), are allyl­ated caged compounds. In (1), the carbon atoms bearing the allyl groups are far apart [2.9417 (17) Å], hence the expected ring-closing metathesis (RCM) protocol failed to give a ring-closing product. When these carbon atoms are connected by a C—C bond as in (2), the distance between them is much smaller [1.611 (3) Å] and consequently the RCM process was successful. The caged carbon skeleton of (1) can be described as a fusion of four five-membered rings and one six-membered ring. All four five-membered rings exhibit envelope conformations. The structure of compound (2) consists of four five-membered rings, of which two are cyclo­penta­none rings bonded at the 2, 4 and 5 positions and linked at the 3-carbons by a methyl­ene bridge. It also consists of one four-membered and two six-membered rings. All four five-membered rings adopt envelope conformations. In the crystal of (1), mol­ecules are linked via C—H⋯O hydrogen bonds, forming sheets lying parallel to (010). In the crystal of (2), mol­ecules are linked via C—H⋯O hydrogen bonds forming chains along [100].

CCDC references: 832290; 963826

1. Chemical context

Caged mol­ecules are much sought after chemical entities due to their diverse applications such as high-energy materials, drug inter­mediates and starting materials for complex natural products (Marchand, 1989a[Marchand, A. P. (1989a). Chem. Rev. 89, 997-1010.],b[Marchand, A. P. (1989b). Chem. Rev. 89, 1011-1033.]; Mehta & Srikrishna, 1997[Mehta, G. & Srikrishna, A. (1997). Chem. Rev. 97, 671-720.]). The intricacies involved in the structural frame of caged mol­ecules, such as deformation of ideal C—C bond angle and other unusual structural features, make them challenging synthetic targets (Olah, 1990[Olah, G. (1990). Cage Hydrocarbons. New York: Wiley.]; Osawa & Yonemitsu, 1992[Osawa, E. & Yonemitsu, O. (1992). Carbocyclic Caged Compounds. New York: VCH.]). Caged mol­ecules are strained due to the rigid geometrical features and they exhibit inter­esting properties (Von et al., 1986[Von, I., Hargittai, I. & Hargittai, M. (1986). Symmetry Through the Eyes of a Chemist. New York: Wiley.]): the high negative heat of combustion and elevated positive heat of formation for caged compounds reveal the strain involved in their mol­ecular architecture.

[Scheme 1]

In connection with our inter­est in designing new varieties of caged compounds, we have synthesized several functionalized derivatives of penta­cyclo [5.4.0.02,6.03,10.05,9]undecane (PCUD) systems (Kotha & Dipak, 2006[Kotha, S. & Dipak, M. K. (2006). Chem. Eur. J. 12, 4446-4450.]; Kotha et al., 2010[Kotha, S., Seema, V., Singh, K. & Deodhar, K. D. (2010). Tetrahedron Lett. 51, 2301-2304.]). Herein, we report on the crystal structures of the title compounds, (1) and (2). These compounds, and their reactions mentioned in this article, are known in the literature (Kotha et al., 1999[Kotha, S., Manivannan, E. & Sreenivasachary, N. (1999). J. Chem. Soc. Perkin Trans. 1, pp. 2845-2848.], 2006[Kotha, S. & Dipak, M. K. (2006). Chem. Eur. J. 12, 4446-4450.]) but their crystal structures have not previously been reported.

When diallyl tetra­cyclic dione (1) was subjected to ring-closing metathesis (RCM), the expected ring-closing product (3) was not obtained, Fig. 1[link]. Whereas, compound (2) successfully underwent RCM to yield the desired ring-closing product (4), see Fig. 1[link]. Further, when compound (1) was subjected to cross metathesis (CM) with but-2-ene-1,4-diallyl acetate (7) in the presence of Grubbs catalyst (Fig. 2[link]), the di­acetate (5) was formed in 55% yield. Under similar reaction conditions, the penta­cyclic dione (2) did not deliver the cross-coupled product (6), but instead the RCM product (4) was formed, see Fig. 1[link]. To gain insight about these observations, the crystal structure determinations of compounds (1) and (2) were undertaken.

[Figure 1]
Figure 1
Synthesis of cage systems (1) and (2).
[Figure 2]
Figure 2
Various Grubbs catalysts used for ring-closing metathesis (RCM).

2. Structural commentary

The caged carbon skeleton of (1), Fig. 3[link], can be described as a fusion of four five-membered rings and one six-membered ring, the latter having a boat conformation. All four five-membered rings exhibit envelope conformations, with atoms C3, twice C17, and C11 as the flap atoms of the various rings. Compound (1) is symmetrically substituted with two allyl groups at atoms C5 and C10. The few crystal structures of PCUD compounds that are recorded in Cambridge Structural Database (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) show no bridging route through the substituents that link the C-atoms [e.g. C1 to C9, Fig. 3[link]]. These compounds are substituted at C1 and/or C9 so that these mol­ecules form the open mouth of the cage. The tetra­cyclic compound (1) shows symmetrical substitution with keto moieties at atoms C1 and C9.

[Figure 3]
Figure 3
A view of the mol­ecular structure of compound (1), with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

The C—C strained bond angles in (1) vary from 95.31 (10) to 125.21 (14)°, deviating from the ideal tetra­hedral angle of 109.5°. Previous studies showed that PCUD caged compounds normally display C—C bond lengths which deviate from expected value of 1.54 Å (Bott et al., 1998[Bott, S. G., Marchand, A. P., Alihodzic, S. & Kumar, K. A. (1998). J. Chem. Crystallogr. 28, 251-258.]; Flippen-Anderson et al., 1991[Flippen-Anderson, J. L., George, C., Gilardi, R., Zajac, W. W., Walters, T. R., Marchand, A., Dave, P. R. & Arney, B. E. (1991). Acta Cryst. C47, 813-817.]; Linden et al., 2005[Linden, A., Romański, J., Mlostoń, G. & Heimgartner, H. (2005). Acta Cryst. C61, o221-o226.]; Kruger et al., 2005[Kruger, H. G., Rademeyer, M. & Ramdhani, R. (2005). Acta Cryst. E61, o3968-o3970.]). The structure of (1) also exhibits unusual Csp3—Csp3 single-bond lengths ranging from 1.5092 (19) Å to 1.5935 (19) Å. The bond C2—C10, which is parallel and immediately adjacent to C1—C9 axis, was found to be longer, with a value of 1.5935 (19) Å. The increase in bond length can be the result of stretching strain commenced by the open mouth of the cage formed by carbonyls bearing carbon atoms, i.e. C1 and C9. Similar observations were made in compound (2), i.e. 1.597 (4) Å for C5—C10.

The structure of compound (2), Fig. 4[link], consists of four five-membered rings, of which two are cyclo­penta­none rings, bonded at the 2, 4 and 5 positions and linked at the 3-carbons by a methyl­ene bridge. It also consists of one four-membered and two six-membered rings, the latter both having a boat conformation. All four five-membered rings adopt envelope conformations, with atoms C5, twice C11, and C10 as the flaps atoms of the various rings. Bonds C4—C11 and C7—C15, corresponding to 1.522 (4) and 1.522 (3) Å, respectively, are the shortest. The longest C—C bonds i.e. C2—C7 [1.611 (3) Å] and C5—C10 [1.597 (4) Å], along with C2—C3, C3—C4 and C7—C8 exceed the expected bond-length value of 1.54 Å. The bonds involving the bridge-head atom C11 are shorter than expected; C9—C11 and C4—C11 being 1.523 (4) and 1.522 (4) Å, respectively. The tetra­hedral bond angle C8—C7—C2 is the most strained with the smallest angle of 88.77 (17)° and the C15—C7—C8 bond angle of 119.6 (2)° is the largest one, again showing considerable deviation from the standard value of 109.5°.

[Figure 4]
Figure 4
A view of the mol­ecular structure of compound (2), with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

It was anti­cipated that the two allyl groups present in (1) would undergo RCM to generate a new penta­cyclic system (3) (Fig. 1[link]). However, it was observed that even under forcing reaction conditions, (1) did not generate the expected RCM product, whereas compound (2) underwent an RCM sequence smoothly to give (4) in good yield (Fig. 1[link]). It was found that the allyl-bearing carbon atoms in tetra­cyclic system (1) are too far apart [C5—C13 = 2.9417 (17) Å] and we believe that due to this reason, the RCM protocol failed. When these carbon atoms are bonded, the distance between them was found to be smaller. Thus in (2), the distance between the bonded atoms C2—C7 is 1.611 (3) Å.

During CM, Fig. 1[link], dione (2) was reacted with but-2-ene-1,4-diallyl acetate (7) to produce cross-coupling product (6). However, (2) failed to deliver the CM product, but under similar conditions, (1) successfully gave the di­acetate (5). In the present scenario, the distance between the allyl-bearing carbon atoms in (1) and (2) has been correlated to understand the reactivity pattern. When the distance between these carbon atoms is large as in the case of (1), the CM product is preferred over RCM, and when the distance is smaller, the RCM product is predominant over the CM product.

The conclusion is that, as the C5—C13 separation in (1) is large [2.9417 (17) Å], the carbon atoms bearing the allyl groups are far apart in this tetra­cyclic system, and the expected ring-closing metathesis (RCM) protocol failed to give the ring-closing product (3), Fig. 1[link]. When these carbon atoms are connected by a C—C bond as in (2), the C2—C7 bond distance was found to be much smaller [1.611 (3) Å], and consequently the RCM process was successful giving the diallyl compound (4), Fig. 1[link].

3. Supra­molecular features

In the crystal of (1), mol­ecules are linked via C—H⋯O hydrogen bonds, forming sheets lying parallel to (010); see Fig. 5[link] and Table 1[link].

Table 1
Hydrogen-bond geometry (Å, °) for (1)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C8—H8B⋯O2i 0.95 2.42 3.3532 (18) 168
C11—H11⋯O1ii 1.00 2.49 3.4815 (16) 173
C16—H16B⋯O1iii 0.95 2.51 3.455 (2) 177
Symmetry codes: (i) x, y, z-1; (ii) x-1, y, z; (iii) [x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].
[Figure 5]
Figure 5
A view along the b axis of the crystal packing of compound (1). Hydrogen bonds are shown as dashed lines (see Table 1[link] for details; only the H atoms involved in these hydrogen bonds are shown).

In the crystal of (2), mol­ecules are linked via C—H⋯O hydrogen bonds, forming chains along [100]; see Fig. 6[link] and Table 2[link].

Table 2
Hydrogen-bond geometry (Å, °) for (2)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C9—H9⋯O2i 1.00 2.44 3.412 (3) 165
C15—H15B⋯O2ii 0.99 2.43 3.383 (3) 160
Symmetry codes: (i) -x+1, -y, -z+2; (ii) -x, -y, -z+2.
[Figure 6]
Figure 6
A view along the c axis of the crystal packing of compound (2). Hydrogen bonds are shown as dashed lines (see Table 2[link] for details; only the H atoms involved in these hydrogen bonds are shown).

4. Synthesis and crystallization

Compounds (1) and (2) were prepared by the procedures reported in the literature (Kotha et al., 1999[Kotha, S., Manivannan, E. & Sreenivasachary, N. (1999). J. Chem. Soc. Perkin Trans. 1, pp. 2845-2848.] and Kotha et al., 2006[Kotha, S. & Dipak, M. K. (2006). Chem. Eur. J. 12, 4446-4450.], respectively) and their melting points were compared with the reported values. In addition, their identity was confirmed by NMR spectroscopic data.

Compound (1): The crude compound (1) was obtained after reaction work-up and was purified using silica gel column chromatography (3% EtOAc/petroleum ether). Colourless crystals were isolated when the solvent was allowed to evaporate (m.p. 356.15–357.15 K; literature m.p. 357.15–358.15 K).

Compound (2): The crude compound (2) was obtained after reaction work-up and was purified using silica gel column chromatography (5% EtOAc/petroleum ether). Colourless crystals were isolated when the solvent was allowed to evaporate (m.p. 353.15–354.15 K; literature m.p. 353.15–354.15 K).

5. Refinement

Crystal data, data collection and structure refinement details of compounds (1) and (2) are summarized in the Table 3[link]. For both the compounds all H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.95–1.00 Å and with Uiso(H) = 1.2Ueq(C).

Table 3
Experimental details

  (1) (2)
Crystal data
Chemical formula C17H20O2 C17H18O2
Mr 256.33 254.31
Crystal system, space group Monoclinic, P21/c Monoclinic, P21/c
Temperature (K) 150 150
a, b, c (Å) 7.8006 (3), 17.9581 (7), 10.1032 (4) 8.7041 (5), 18.3992 (9), 9.0906 (6)
β (°) 99.664 (4) 113.043 (7)
V (Å3) 1395.21 (9) 1339.69 (13)
Z 4 4
Radiation type Mo Kα Mo Kα
μ (mm−1) 0.08 0.08
Crystal size (mm) 0.29 × 0.25 × 0.21 0.32 × 0.28 × 0.23
 
Data collection
Diffractometer Oxford Diffraction Xcalibur-S Oxford Diffraction Xcalibur-S
Absorption correction Multi-scan (CrysAlis RED; Oxford Diffraction, 2006[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]) Multi-scan (CrysAlis RED; Oxford Diffraction, 2006[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.])
Tmin, Tmax 0.978, 0.984 0.975, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections 9836, 2448, 1988 8644, 2356, 1625
Rint 0.020 0.036
(sin θ/λ)max (Å−1) 0.595 0.595
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.099, 1.06 0.059, 0.188, 1.10
No. of reflections 2448 2356
No. of parameters 172 172
H-atom treatment H-atom parameters constrained H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.20, −0.15 0.10, −0.34
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2006[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC references: 832290; 963826

Crystal structure: contains datablocks 1, 2, global. DOI: 10.1107/S1600536814023149/su5002sup1.cif

Structure factors: contains datablock 1. DOI: 10.1107/S1600536814023149/su50021sup2.hkl

Structure factors: contains datablock 2. DOI: 10.1107/S1600536814023149/su50022sup3.hkl

Supporting information file. DOI: 10.1107/S1600536814023149/su50022sup4.cml

checkCIF report


Chemical context top

Caged molecules are much sought after chemical entities due to their diverse applications such as high-energy materials, drug inter­mediates and starting materials for complex natural products (Marchand, 1989a,b; Mehta & Srikrishna, 1997). The intricacies involved in the structural frame of caged molecules, such as deformation of ideal C—C bond angle and other unusual structural features, make them challenging synthetic targets (Olah, 1990; Osawa & Yonemitsu, 1992). Caged molecules are strained due to the rigid geometrical features and they exhibit inter­esting properties (Von et al., 1986): the high negative heat of combustion and elevated positive heat of formation for caged compounds reveal the strain involved in their molecular architecture.

In connection with our inter­est in designing novel caged compounds, we have synthesized several functionalized derivatives of penta­cyclo [5.4.0.02,6.03,10.05,9]undecane (PCUD) systems (Kotha & Dipak, 2006; Kotha et al., 2010). Herein, we report on the crystal structures of the title compounds, (1) and (2). These compounds, and their reactions mentioned in this article, are known in the literature (Kotha et al., 1999, 2006) but their crystal structures have not previously been reported.

When di­allyl tetra­cyclic dione (1) was subjected to ring-closing metathesis (RCM), the expected ring-closing product (3) was not obtained, Fig. 1. Whereas, compound (2) successfully underwent RCM to yield the desired ring-closing product (4), see Fig. 1. Further, when compound (1) was subjected to cross metathesis (CM) with but-2-ene-1,4-di­allyl acetate (7) in the presence of Grubbs catalyst (Fig. 2), the di­acetate (5) was formed in 55% yield. Under similar reaction conditions, the penta­cyclic dione (2) did not deliver the cross-coupled product (6), but instead the RCM product (4) was formed, see Fig. 1. To gain insight about these observations, the crystal structure determinations of compounds (1) and (2) were undertaken.

Structural commentary top

The caged carbon skeleton of (1), Fig. 3, can be described as a fusion of four five-membered rings and one six-membered ring, the latter having a boat conformation. All four five-membered rings exhibit envelope conformations, with atoms C3, twice C17, and C11 as the flap atoms of the various rings. Compound (1) is symmetrically substituted with two allyl groups at atoms C5 and C10. The few crystal structures of PCUD compounds that are recorded in Cambridge Structural Database (Groom & Allen, 2014) show no bridging route through the substituents that link the C-atoms [e.g. C1 to C9, Fig. 3]. These compounds are substituted at C1 and/or C9 so that these molecules form the open mouth of the cage. The tetra­cyclic compound (1) shows symmetrical substitution with keto moieties at atoms C1 and C9.

The C—C strained bond angles in (1) vary from 95.31 (10) to 125.21 (14)°, deviating from the ideal tetra­hedral angle of 109.5°. Previous studies showed that PCUD caged compounds normally display C—C bond lengths which deviate from expected value of 1.54 Å (Bott et al., 1998; Flippen-Anderson et al., 1991; Linden et al., 2005; Kruger et al. 2005). The structure of (1) also exhibits unusual Csp3—Csp3 single-bond lengths ranging from 1.5092 (19) Å to 1.5935 (19) Å. The bond C2—C10, which is parallel and immediately adjacent to C1—C9 axis, was found to be longer at value 1.5935 (19) Å. The increase in bond length can be the result of stretching strain commenced by the open mouth of the cage formed by carbonyl-bearing carbons i.e. atoms C1 and C9. Similar observations were made in compound (2), i.e. 1.597 (4) Å for C5—C10.

The structure of compound (2), Fig. 4, consists of four five-membered rings, of which two are cyclo­penta­none rings, bonded at the 2, 4 and 5 positions and linked at the 3-carbons by a methyl­ene bridge. It also consists of one four-membered and two six-membered rings, the latter both having a boat conformation. All four five-membered rings adopt envelope conformations, with atoms C5, twice C11, and C10 as the flaps atoms of the various rings. Bonds C4—C11 and C7—C15, corresponding to 1.522 (4) and 1.522 (3) Å, respectively, are the shortest. The longest C—C bonds i.e. C2—C7 [1.611 (3) Å] and C5—C10 [1.597 (4) Å], along with C2—C3, C3—C4 and C7—C8 exceed the expected bond-length value of 1.54 Å. The bonds involving the bridge-head atom C11 are shorter than expected; C9—C11 and C4—C11 being 1.523 (4) and 1.522 (4) Å, respectively. The tetra­hedral bond angle C8—C7—C2 is the most strained with the smallest angle of 88.77 (17)° and the C15—C7—C8 bond angle of 119.6 (2)° is the largest one, again showing considerable deviation from the standard value of 109.5°.

It was anti­cipated that the two allyl groups present in (1) would undergo RCM to generate a new novel penta­cyclic system (3) (Fig. 1). However, it was observed that even under forcing reaction conditions, (1) did not generate the expected RCM product, whereas compound (2) underwent an RCM sequence smoothly to give (4) in good yield (Fig. 1). It was found that the allyl-bearing carbons in tetra­cyclic system (1) are too far apart [C5—C13 = 2.9417 (17) Å] and we believe that due to this reason, the RCM protocol failed. When these carbons are bonded, the distance between them was found to be smaller. Thus in (2), the distance between the bonded atoms C2—C7 is 1.611 (3) Å.

During CM, Fig. 1, dione (2) was reacted with but-2-ene-1,4-di­allyl acetate (7) to produce cross-coupling product (6). However, (2) failed to deliver the CM product, but under similar conditions, (1) successfully gave the di­acetate (5). In the present scenario, the distance between the allyl-bearing carbons in (1) and (2) has been correlated to understand the reactivity pattern. When the distance between these carbon atoms is large as in the case of (1), the RCM product is preferred over CM, and when the distance is smaller, the CM product is predominant over the RCM product.

The conclusion is that, as the C5—C13 separation in (1) is large [2.9417 (17) Å], the carbon atoms bearing the allyl groups are far apart in this tetra­cyclic system, and the expected ring-closing metathesis (RCM) protocol failed to give the ring-closing product (3), Fig. 1. When these carbon atoms are connected by a C—C bond as in (2), the C2—C7 bond distance was found to be much smaller [1.611 (3) Å], and consequently the RCM process was successful giving the di­allyl compound (4), Fig. 1.

Supra­molecular features top

In the crystal of (1), molecules are linked via C—H···O hydrogen bonds, forming sheets lying parallel to (010); see Fig. 5 and Table 1.

In the crystal of (2), molecules are linked via C—H···O hydrogen bonds, forming chains along [100]; see Fig. 6 and Table 2.

Synthesis and crystallization top

Compounds (1) and (2) were prepared by the procedures reported in the literature (Kotha et al., 1999 and Kotha et al., 2006, respectively) and their melting points were compared with the reported values. In addition, their identity was confirmed by NMR spectroscopic data.

Compound (1): The crude compound (1) was obtained after reaction work-up and was purified using silica gel column chromatography (3% EtOAc/petroleum ether). White crystals were isolated when the solvent was allowed to evaporate (m.p. 356.15–357.15 K; literature m.p. 357.15–358.15 K).

Compound (2): The crude compound (2) was obtained after reaction work-up and was purified using silica gel column chromatography (5% EtOAc/petroleum ether). White crystals were isolated when the solvent was allowed to evaporate (m.p. 353.15–354.15 K; literature m.p. 353.15–354.15 K).

Refinement top

Crystal data, data collection and structure refinement details of compounds (1) and (2) are summarized in the Table 3. For both the compounds all H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.95–1.00 Å and with Uiso(H) = 1.2Ueq(C).

Related literature top

For related literature, see: Kotha & Dipak (2006); Mehta & Srikrishna (1997); Olah (1990); Osawa & Yonemitsu (1992); Von et al. (1986).

Computing details top

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
Synthesis of cage systems (1) and (2).

Various Grubbs catalysts used for ring-closing metathesis (RCM).

A view of the molecular structure of compound (1), with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

A view of the molecular structure of compound (2), with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

A view along the b axis of the crystal packing of compound (1). Hydrogen bonds are shown as dashed lines (see Table 1 for details; only the H atoms involved in these hydrogen bonds are shown).

A view along the c axis of the crystal packing of compound (2). Hydrogen bonds are shown as dashed lines (see Table 2 for details; only the H atoms involved in these hydrogen bonds are shown).
(1) 3,6-Diallyltetracyclo[6.3.0.04,11.05,9]undeca-2,7-dione top
Crystal data top
C17H20O2F(000) = 552
Mr = 256.33Dx = 1.220 Mg m−3
Monoclinic, P21/cMelting point = 358.15–357.15 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.8006 (3) ÅCell parameters from 6517 reflections
b = 17.9581 (7) Åθ = 3.0–32.7°
c = 10.1032 (4) ŵ = 0.08 mm−1
β = 99.664 (4)°T = 150 K
V = 1395.21 (9) Å3Block, colourless
Z = 40.29 × 0.25 × 0.21 mm
Data collection top
Oxford Diffraction Xcalibur-S
diffractometer		2448 independent reflections
Radiation source: Enhance (Mo) X-ray Source1988 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
Detector resolution: 15.9948 pixels mm-1θmax = 25.0°, θmin = 3.1°
ω/θ scanh = −8→9
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		k = −16→21
Tmin = 0.978, Tmax = 0.984l = −12→11
9836 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0593P)2 + 0.1101P]
where P = (Fo2 + 2Fc2)/3
2448 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.20 e Å−3
0 restraintsΔρmin = −0.15 e Å−3
Crystal data top
C17H20O2V = 1395.21 (9) Å3
Mr = 256.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.8006 (3) ŵ = 0.08 mm−1
b = 17.9581 (7) ÅT = 150 K
c = 10.1032 (4) Å0.29 × 0.25 × 0.21 mm
β = 99.664 (4)°
Data collection top
Oxford Diffraction Xcalibur-S
diffractometer		2448 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		1988 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.984Rint = 0.020
9836 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.06Δρmax = 0.20 e Å−3
2448 reflectionsΔρmin = −0.15 e Å−3
172 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O11.08309 (12)0.09661 (6)0.38127 (10)0.0465 (3)
O20.76657 (13)0.19086 (6)0.53385 (10)0.0490 (3)
C10.94097 (16)0.08946 (7)0.31302 (13)0.0324 (3)
C20.79906 (17)0.03752 (7)0.34071 (14)0.0356 (3)
H20.8455−0.00840.39010.043*
C30.69710 (16)0.02075 (7)0.20005 (14)0.0346 (3)
H30.7485−0.01870.14880.042*
C40.69283 (15)0.10017 (6)0.13886 (12)0.0268 (3)
H40.65800.09870.03900.032*
C50.87980 (15)0.12806 (7)0.17908 (12)0.0286 (3)
H50.88150.18340.19100.034*
C60.99967 (17)0.10487 (8)0.07944 (13)0.0357 (3)
H6A1.12160.11630.11930.043*
H6B0.99060.05040.06540.043*
C70.95710 (17)0.14291 (8)−0.05317 (15)0.0394 (3)
H70.97480.1952−0.05520.047*
C80.89716 (18)0.10982 (8)−0.16722 (15)0.0434 (4)
H8A0.87770.0576−0.16940.052*
H8B0.87320.1381−0.24770.052*
C90.69334 (16)0.16148 (8)0.43169 (13)0.0330 (3)
C100.65726 (16)0.07918 (8)0.41034 (13)0.0358 (3)
H100.63610.05350.49400.043*
C110.49650 (16)0.07774 (7)0.29843 (14)0.0342 (3)
H110.38230.08530.32900.041*
C120.55016 (15)0.13988 (6)0.20733 (12)0.0261 (3)
H120.44920.15610.13890.031*
C130.61320 (15)0.20307 (7)0.30522 (12)0.0279 (3)
H130.70380.23330.27060.034*
C140.46574 (17)0.25372 (7)0.33636 (13)0.0360 (3)
H14A0.37500.22270.36700.043*
H14B0.51250.28810.41020.043*
C150.38610 (19)0.29780 (7)0.21698 (15)0.0394 (4)
H150.46180.32690.17340.047*
C160.2208 (2)0.29971 (9)0.16746 (18)0.0532 (4)
H16A0.14070.27140.20810.064*
H16B0.18030.32940.09070.064*
C170.51225 (18)0.00663 (7)0.22074 (16)0.0424 (4)
H17A0.5013−0.03860.27460.051*
H17B0.42910.00460.13520.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0281 (5)0.0757 (8)0.0339 (6)−0.0008 (5)−0.0002 (4)0.0008 (5)
O20.0512 (6)0.0650 (7)0.0274 (6)−0.0010 (5)−0.0029 (5)−0.0055 (5)
C10.0255 (7)0.0406 (8)0.0306 (7)0.0041 (6)0.0033 (6)−0.0027 (6)
C20.0335 (7)0.0333 (7)0.0386 (8)0.0046 (5)0.0016 (6)0.0111 (6)
C30.0334 (7)0.0258 (7)0.0431 (8)0.0012 (5)0.0015 (6)−0.0007 (6)
C40.0275 (6)0.0261 (6)0.0256 (7)0.0013 (5)0.0010 (5)−0.0020 (5)
C50.0267 (6)0.0304 (6)0.0290 (7)0.0007 (5)0.0053 (5)−0.0008 (5)
C60.0317 (7)0.0421 (8)0.0344 (8)0.0069 (6)0.0086 (6)0.0024 (6)
C70.0412 (8)0.0401 (8)0.0402 (8)0.0048 (6)0.0163 (6)0.0076 (6)
C80.0449 (8)0.0500 (9)0.0363 (8)0.0101 (7)0.0103 (7)0.0108 (7)
C90.0272 (6)0.0474 (8)0.0252 (7)−0.0008 (6)0.0065 (5)−0.0015 (6)
C100.0323 (7)0.0447 (8)0.0309 (8)−0.0016 (6)0.0072 (6)0.0133 (6)
C110.0252 (6)0.0372 (7)0.0401 (8)−0.0042 (5)0.0052 (6)0.0059 (6)
C120.0236 (6)0.0279 (6)0.0258 (7)0.0000 (5)0.0008 (5)−0.0004 (5)
C130.0279 (6)0.0315 (7)0.0246 (7)−0.0013 (5)0.0051 (5)−0.0018 (5)
C140.0375 (7)0.0385 (7)0.0332 (8)0.0019 (6)0.0097 (6)−0.0088 (6)
C150.0467 (8)0.0267 (7)0.0478 (9)0.0068 (6)0.0163 (7)−0.0010 (6)
C160.0525 (10)0.0492 (9)0.0563 (10)0.0161 (7)0.0039 (8)0.0003 (8)
C170.0376 (8)0.0295 (7)0.0580 (10)−0.0074 (6)0.0019 (7)0.0040 (6)
Geometric parameters (Å, º) top
O1—C11.2101 (15)C8—H8B0.9500
O2—C91.2133 (16)C9—C101.5132 (19)
C1—C21.5092 (19)C9—C131.5209 (17)
C1—C51.5239 (18)C10—C111.5413 (18)
C2—C31.5374 (19)C10—H101.0000
C2—C101.5935 (19)C11—C171.515 (2)
C2—H21.0000C11—C121.5483 (18)
C3—C171.5127 (19)C11—H111.0000
C3—C41.5527 (17)C12—C131.5310 (16)
C3—H31.0000C12—H121.0000
C4—C51.5311 (16)C13—C141.5398 (17)
C4—C121.5761 (17)C13—H131.0000
C4—H41.0000C14—C151.4886 (19)
C5—C61.5418 (18)C14—H14A0.9900
C5—H51.0000C14—H14B0.9900
C6—C71.4909 (19)C15—C161.303 (2)
C6—H6A0.9900C15—H150.9500
C6—H6B0.9900C16—H16A0.9500
C7—C81.311 (2)C16—H16B0.9500
C7—H70.9500C17—H17A0.9900
C8—H8A0.9500C17—H17B0.9900
O1—C1—C2126.17 (12)C9—C10—C11103.29 (10)
O1—C1—C5125.31 (12)C9—C10—C2113.28 (10)
C2—C1—C5108.40 (10)C11—C10—C2102.00 (11)
C1—C2—C3103.38 (11)C9—C10—H10112.5
C1—C2—C10112.13 (11)C11—C10—H10112.5
C3—C2—C10102.14 (10)C2—C10—H10112.5
C1—C2—H2112.8C17—C11—C10105.51 (11)
C3—C2—H2112.8C17—C11—C12104.24 (11)
C10—C2—H2112.8C10—C11—C1298.98 (9)
C17—C3—C2105.21 (11)C17—C11—H11115.4
C17—C3—C4104.58 (10)C10—C11—H11115.4
C2—C3—C499.28 (10)C12—C11—H11115.4
C17—C3—H3115.3C13—C12—C11103.87 (10)
C2—C3—H3115.3C13—C12—C4116.42 (9)
C4—C3—H3115.3C11—C12—C4102.48 (9)
C5—C4—C3103.83 (9)C13—C12—H12111.1
C5—C4—C12116.54 (9)C11—C12—H12111.1
C3—C4—C12102.15 (10)C4—C12—H12111.1
C5—C4—H4111.2C9—C13—C12102.76 (10)
C3—C4—H4111.2C9—C13—C14109.52 (10)
C12—C4—H4111.2C12—C13—C14113.56 (10)
C1—C5—C4103.25 (10)C9—C13—H13110.3
C1—C5—C6108.85 (10)C12—C13—H13110.3
C4—C5—C6113.17 (10)C14—C13—H13110.3
C1—C5—H5110.4C15—C14—C13111.91 (11)
C4—C5—H5110.4C15—C14—H14A109.2
C6—C5—H5110.4C13—C14—H14A109.2
C7—C6—C5113.27 (11)C15—C14—H14B109.2
C7—C6—H6A108.9C13—C14—H14B109.2
C5—C6—H6A108.9H14A—C14—H14B107.9
C7—C6—H6B108.9C16—C15—C14125.21 (14)
C5—C6—H6B108.9C16—C15—H15117.4
H6A—C6—H6B107.7C14—C15—H15117.4
C8—C7—C6125.09 (13)C15—C16—H16A120.0
C8—C7—H7117.5C15—C16—H16B120.0
C6—C7—H7117.5H16A—C16—H16B120.0
C7—C8—H8A120.0C3—C17—C1195.31 (10)
C7—C8—H8B120.0C3—C17—H17A112.7
H8A—C8—H8B120.0C11—C17—H17A112.7
O2—C9—C10126.56 (12)C3—C17—H17B112.7
O2—C9—C13124.72 (12)C11—C17—H17B112.7
C10—C9—C13108.63 (10)H17A—C17—H17B110.2
O1—C1—C2—C3−151.97 (13)C1—C2—C10—C11111.21 (11)
C5—C1—C2—C324.34 (13)C3—C2—C10—C111.15 (12)
O1—C1—C2—C1098.75 (15)C9—C10—C11—C17149.32 (10)
C5—C1—C2—C10−84.94 (13)C2—C10—C11—C1731.59 (12)
C1—C2—C3—C17−150.16 (10)C9—C10—C11—C1241.72 (12)
C10—C2—C3—C17−33.58 (12)C2—C10—C11—C12−76.02 (11)
C1—C2—C3—C4−42.17 (12)C17—C11—C12—C13−155.36 (10)
C10—C2—C3—C474.40 (11)C10—C11—C12—C13−46.73 (12)
C17—C3—C4—C5154.13 (11)C17—C11—C12—C4−33.76 (12)
C2—C3—C4—C545.65 (12)C10—C11—C12—C474.87 (11)
C17—C3—C4—C1232.55 (12)C5—C4—C12—C130.96 (15)
C2—C3—C4—C12−75.94 (10)C3—C4—C12—C13113.34 (11)
O1—C1—C5—C4−179.33 (13)C5—C4—C12—C11−111.63 (11)
C2—C1—C5—C44.32 (13)C3—C4—C12—C110.75 (11)
O1—C1—C5—C660.17 (17)O2—C9—C13—C12176.67 (12)
C2—C1—C5—C6−116.18 (11)C10—C9—C13—C12−6.41 (12)
C3—C4—C5—C1−31.17 (12)O2—C9—C13—C14−62.32 (16)
C12—C4—C5—C180.25 (12)C10—C9—C13—C14114.61 (11)
C3—C4—C5—C686.34 (12)C11—C12—C13—C933.19 (11)
C12—C4—C5—C6−162.24 (10)C4—C12—C13—C9−78.60 (12)
C1—C5—C6—C7−176.82 (11)C11—C12—C13—C14−85.01 (12)
C4—C5—C6—C769.01 (15)C4—C12—C13—C14163.19 (10)
C5—C6—C7—C8−113.80 (15)C9—C13—C14—C15178.13 (11)
O2—C9—C10—C11154.12 (13)C12—C13—C14—C15−67.64 (14)
C13—C9—C10—C11−22.73 (13)C13—C14—C15—C16126.15 (15)
O2—C9—C10—C2−96.36 (15)C2—C3—C17—C1151.81 (12)
C13—C9—C10—C286.79 (12)C4—C3—C17—C11−52.28 (12)
C1—C2—C10—C90.89 (15)C10—C11—C17—C3−51.04 (12)
C3—C2—C10—C9−109.18 (12)C12—C11—C17—C352.70 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8B···O2i0.952.423.3532 (18)168
C11—H11···O1ii1.002.493.4815 (16)173
C16—H16B···O1iii0.952.513.455 (2)177
Symmetry codes: (i) x, y, z−1; (ii) x−1, y, z; (iii) x−1, −y+1/2, z−1/2.
(2) 1,7-Diallylpentacyclo[5.4.0.02,6. 03,10.05,9]undecane-8,11-dione top
Crystal data top
C17H18O2F(000) = 544
Mr = 254.31Dx = 1.261 Mg m−3
Monoclinic, P21/cMelting point = 354.15–353.15 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 8.7041 (5) ÅCell parameters from 4211 reflections
b = 18.3992 (9) Åθ = 3.3–32.4°
c = 9.0906 (6) ŵ = 0.08 mm−1
β = 113.043 (7)°T = 150 K
V = 1339.69 (13) Å3Block, colourless
Z = 40.32 × 0.28 × 0.23 mm
Data collection top
Oxford Diffraction Xcalibur-S
diffractometer		2356 independent reflections
Radiation source: Enhance (Mo) X-ray Source1625 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 15.9948 pixels mm-1θmax = 25.0°, θmin = 3.3°
ω/θ scansh = −9→10
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		k = −21→21
Tmin = 0.975, Tmax = 0.982l = −10→10
8644 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.188H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.1199P)2]
where P = (Fo2 + 2Fc2)/3
2356 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.10 e Å−3
0 restraintsΔρmin = −0.34 e Å−3
Crystal data top
C17H18O2V = 1339.69 (13) Å3
Mr = 254.31Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.7041 (5) ŵ = 0.08 mm−1
b = 18.3992 (9) ÅT = 150 K
c = 9.0906 (6) Å0.32 × 0.28 × 0.23 mm
β = 113.043 (7)°
Data collection top
Oxford Diffraction Xcalibur-S
diffractometer		2356 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		1625 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.982Rint = 0.036
8644 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.188H-atom parameters constrained
S = 1.10Δρmax = 0.10 e Å−3
2356 reflectionsΔρmin = −0.34 e Å−3
172 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1−0.1367 (2)0.06672 (11)0.5971 (2)0.0424 (6)
O20.2051 (2)−0.02964 (10)0.9446 (2)0.0432 (6)
C1−0.0014 (3)0.09420 (13)0.6688 (3)0.0304 (6)
C20.0464 (3)0.14322 (12)0.8151 (3)0.0253 (6)
C30.1827 (3)0.19321 (13)0.7979 (3)0.0248 (6)
H30.17010.24660.80990.030*
C40.2176 (3)0.16845 (14)0.6509 (3)0.0322 (6)
H40.16840.20000.55410.039*
C50.1520 (3)0.08931 (14)0.6303 (3)0.0336 (7)
H50.13100.06780.52310.040*
C60.2263 (3)0.03044 (14)0.9011 (3)0.0322 (6)
C70.1904 (3)0.10269 (13)0.9618 (3)0.0268 (6)
C80.3217 (3)0.15429 (13)0.9379 (3)0.0267 (6)
H80.38990.18511.03130.032*
C90.4181 (3)0.11108 (14)0.8554 (3)0.0331 (7)
H90.53340.09550.92660.040*
C100.2941 (3)0.04889 (14)0.7757 (3)0.0341 (7)
H100.34540.00660.74250.041*
C110.4068 (3)0.16081 (15)0.7176 (3)0.0377 (7)
H11A0.46510.20770.75440.045*
H11B0.44700.13720.64140.045*
C12−0.1015 (3)0.17601 (13)0.8421 (3)0.0287 (6)
H12A−0.17860.13670.84350.034*
H12B−0.06090.20050.94750.034*
C13−0.1941 (3)0.22985 (15)0.7137 (3)0.0345 (7)
H13−0.24990.21150.60840.041*
C14−0.2046 (4)0.29917 (16)0.7340 (4)0.0441 (8)
H14A−0.15080.31990.83740.053*
H14B−0.26620.32920.64560.053*
C150.1757 (3)0.10004 (14)1.1231 (3)0.0338 (7)
H15A0.15410.14951.15320.041*
H15B0.08030.06871.11530.041*
C160.3326 (4)0.0708 (2)1.2495 (4)0.0542 (9)
H160.34450.01941.25510.065*
C170.4476 (5)0.1061 (2)1.3466 (4)0.0664 (11)
H17A0.44220.15771.34620.080*
H17B0.54190.08181.42190.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0307 (11)0.0387 (12)0.0478 (12)−0.0057 (9)0.0047 (9)−0.0107 (9)
O20.0398 (12)0.0226 (10)0.0648 (14)0.0051 (9)0.0180 (10)0.0092 (9)
C10.0301 (14)0.0206 (13)0.0343 (14)0.0013 (11)0.0059 (12)0.0028 (10)
C20.0248 (13)0.0201 (12)0.0297 (13)0.0025 (10)0.0092 (11)0.0032 (10)
C30.0277 (13)0.0180 (12)0.0290 (13)−0.0009 (10)0.0113 (11)0.0000 (9)
C40.0360 (15)0.0319 (14)0.0305 (13)0.0004 (12)0.0149 (12)0.0021 (11)
C50.0365 (15)0.0324 (15)0.0312 (14)−0.0005 (12)0.0125 (12)−0.0092 (11)
C60.0226 (13)0.0251 (14)0.0426 (15)0.0024 (11)0.0058 (12)0.0022 (11)
C70.0254 (13)0.0222 (13)0.0309 (13)0.0027 (10)0.0089 (11)0.0022 (10)
C80.0254 (13)0.0237 (13)0.0285 (13)−0.0019 (10)0.0080 (11)−0.0041 (10)
C90.0238 (13)0.0363 (15)0.0395 (15)0.0017 (11)0.0127 (12)−0.0053 (12)
C100.0314 (15)0.0274 (14)0.0450 (16)0.0048 (11)0.0166 (13)−0.0066 (11)
C110.0366 (16)0.0394 (16)0.0446 (16)−0.0006 (13)0.0239 (13)−0.0019 (13)
C120.0260 (13)0.0249 (13)0.0359 (14)0.0003 (11)0.0127 (11)0.0030 (11)
C130.0261 (14)0.0387 (16)0.0367 (14)0.0062 (12)0.0100 (12)0.0040 (12)
C140.0397 (17)0.0329 (16)0.0550 (18)0.0086 (13)0.0136 (15)0.0089 (13)
C150.0332 (14)0.0334 (15)0.0358 (14)0.0057 (12)0.0146 (12)0.0085 (12)
C160.0457 (19)0.078 (2)0.0377 (17)0.0160 (18)0.0153 (15)0.0077 (17)
C170.059 (2)0.087 (3)0.051 (2)0.011 (2)0.0193 (19)−0.006 (2)
Geometric parameters (Å, º) top
O1—C11.211 (3)C9—C111.523 (4)
O2—C61.212 (3)C9—C101.545 (4)
C1—C51.510 (4)C9—H91.0000
C1—C21.524 (4)C10—H101.0000
C2—C121.526 (3)C11—H11A0.9900
C2—C31.557 (3)C11—H11B0.9900
C2—C71.611 (3)C12—C131.502 (4)
C3—C81.546 (3)C12—H12A0.9900
C3—C41.550 (4)C12—H12B0.9900
C3—H31.0000C13—C141.297 (4)
C4—C111.522 (4)C13—H130.9500
C4—C51.549 (4)C14—H14A0.9500
C4—H41.0000C14—H14B0.9500
C5—C101.597 (4)C15—C161.498 (4)
C5—H51.0000C15—H15A0.9900
C6—C101.513 (4)C15—H15B0.9900
C6—C71.518 (3)C16—C171.229 (5)
C7—C151.522 (3)C16—H160.9500
C7—C81.565 (4)C17—H17A0.9500
C8—C91.546 (4)C17—H17B0.9500
C8—H81.0000
O1—C1—C5127.7 (2)C11—C9—C10104.6 (2)
O1—C1—C2126.4 (3)C11—C9—C8102.6 (2)
C5—C1—C2105.9 (2)C10—C9—C8101.3 (2)
C1—C2—C12114.5 (2)C11—C9—H9115.5
C1—C2—C3102.7 (2)C10—C9—H9115.5
C12—C2—C3120.4 (2)C8—C9—H9115.5
C1—C2—C7107.84 (19)C6—C10—C9102.7 (2)
C12—C2—C7118.8 (2)C6—C10—C5108.9 (2)
C3—C2—C788.83 (17)C9—C10—C5102.5 (2)
C8—C3—C4102.6 (2)C6—C10—H10113.9
C8—C3—C291.47 (18)C9—C10—H10113.9
C4—C3—C2109.09 (19)C5—C10—H10113.9
C8—C3—H3116.7C4—C11—C995.4 (2)
C4—C3—H3116.7C4—C11—H11A112.7
C2—C3—H3116.7C9—C11—H11A112.7
C11—C4—C5104.6 (2)C4—C11—H11B112.7
C11—C4—C3103.3 (2)C9—C11—H11B112.7
C5—C4—C3101.1 (2)H11A—C11—H11B110.1
C11—C4—H4115.3C13—C12—C2111.4 (2)
C5—C4—H4115.3C13—C12—H12A109.3
C3—C4—H4115.3C2—C12—H12A109.3
C1—C5—C4103.5 (2)C13—C12—H12B109.3
C1—C5—C10107.7 (2)C2—C12—H12B109.3
C4—C5—C10102.0 (2)H12A—C12—H12B108.0
C1—C5—H5114.1C14—C13—C12125.7 (3)
C4—C5—H5114.1C14—C13—H13117.1
C10—C5—H5114.1C12—C13—H13117.1
O2—C6—C10127.2 (2)C13—C14—H14A120.0
O2—C6—C7127.0 (2)C13—C14—H14B120.0
C10—C6—C7105.9 (2)H14A—C14—H14B120.0
C6—C7—C15115.4 (2)C16—C15—C7110.8 (2)
C6—C7—C8102.5 (2)C16—C15—H15A109.5
C15—C7—C8119.6 (2)C7—C15—H15A109.5
C6—C7—C2108.00 (19)C16—C15—H15B109.5
C15—C7—C2118.7 (2)C7—C15—H15B109.5
C8—C7—C288.77 (17)H15A—C15—H15B108.1
C3—C8—C9103.7 (2)C17—C16—C15127.0 (4)
C3—C8—C790.93 (18)C17—C16—H16116.5
C9—C8—C7108.6 (2)C15—C16—H16116.5
C3—C8—H8116.7C16—C17—H17A120.0
C9—C8—H8116.7C16—C17—H17B120.0
C7—C8—H8116.7H17A—C17—H17B120.0
O1—C1—C2—C12−17.7 (4)C4—C3—C8—C9−0.8 (2)
C5—C1—C2—C12160.6 (2)C2—C3—C8—C9109.1 (2)
O1—C1—C2—C3−150.1 (2)C4—C3—C8—C7−110.27 (19)
C5—C1—C2—C328.2 (2)C2—C3—C8—C7−0.32 (18)
O1—C1—C2—C7117.0 (3)C6—C7—C8—C3108.48 (19)
C5—C1—C2—C7−64.7 (2)C15—C7—C8—C3−122.4 (2)
C1—C2—C3—C8−107.72 (19)C2—C7—C8—C30.31 (17)
C12—C2—C3—C8123.5 (2)C6—C7—C8—C93.6 (2)
C7—C2—C3—C80.31 (18)C15—C7—C8—C9132.8 (2)
C1—C2—C3—C4−3.8 (2)C2—C7—C8—C9−104.5 (2)
C12—C2—C3—C4−132.6 (2)C3—C8—C9—C1134.2 (2)
C7—C2—C3—C4104.2 (2)C7—C8—C9—C11129.9 (2)
C8—C3—C4—C11−32.9 (2)C3—C8—C9—C10−73.7 (2)
C2—C3—C4—C11−129.0 (2)C7—C8—C9—C1022.0 (2)
C8—C3—C4—C575.2 (2)O2—C6—C10—C9−135.8 (3)
C2—C3—C4—C5−20.9 (2)C7—C6—C10—C944.1 (2)
O1—C1—C5—C4135.6 (3)O2—C6—C10—C5116.1 (3)
C2—C1—C5—C4−42.6 (2)C7—C6—C10—C5−64.0 (2)
O1—C1—C5—C10−116.8 (3)C11—C9—C10—C6−145.8 (2)
C2—C1—C5—C1064.9 (2)C8—C9—C10—C6−39.4 (2)
C11—C4—C5—C1145.1 (2)C11—C9—C10—C5−32.8 (2)
C3—C4—C5—C138.0 (2)C8—C9—C10—C573.5 (2)
C11—C4—C5—C1033.3 (2)C1—C5—C10—C6−0.5 (3)
C3—C4—C5—C10−73.8 (2)C4—C5—C10—C6108.0 (2)
O2—C6—C7—C1519.1 (4)C1—C5—C10—C9−108.8 (2)
C10—C6—C7—C15−160.8 (2)C4—C5—C10—C9−0.3 (2)
O2—C6—C7—C8150.9 (3)C5—C4—C11—C9−52.5 (2)
C10—C6—C7—C8−29.1 (2)C3—C4—C11—C953.0 (2)
O2—C6—C7—C2−116.4 (3)C10—C9—C11—C452.2 (2)
C10—C6—C7—C263.7 (2)C8—C9—C11—C4−53.2 (2)
C1—C2—C7—C60.0 (3)C1—C2—C12—C13−67.8 (3)
C12—C2—C7—C6132.4 (2)C3—C2—C12—C1355.5 (3)
C3—C2—C7—C6−103.0 (2)C7—C2—C12—C13162.7 (2)
C1—C2—C7—C15−133.8 (2)C2—C12—C13—C14−114.1 (3)
C12—C2—C7—C15−1.3 (3)C6—C7—C15—C1658.3 (3)
C3—C2—C7—C15123.2 (2)C8—C7—C15—C16−64.7 (3)
C1—C2—C7—C8102.7 (2)C2—C7—C15—C16−171.2 (2)
C12—C2—C7—C8−124.9 (2)C7—C15—C16—C1798.4 (4)
C3—C2—C7—C8−0.31 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O2i1.002.443.412 (3)165
C15—H15B···O2ii0.992.433.383 (3)160
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+2.
Hydrogen-bond geometry (Å, º) for (1) top
D—H···AD—HH···AD···AD—H···A
C8—H8B···O2i0.952.423.3532 (18)168
C11—H11···O1ii1.002.493.4815 (16)173
C16—H16B···O1iii0.952.513.455 (2)177
Symmetry codes: (i) x, y, z−1; (ii) x−1, y, z; (iii) x−1, −y+1/2, z−1/2.
Hydrogen-bond geometry (Å, º) for (2) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O2i1.002.443.412 (3)165
C15—H15B···O2ii0.992.433.383 (3)160
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+2.

Experimental details

(1)(2)
Crystal data
Chemical formulaC17H20O2C17H18O2
Mr256.33254.31
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)150150
a, b, c (Å)7.8006 (3), 17.9581 (7), 10.1032 (4)8.7041 (5), 18.3992 (9), 9.0906 (6)
β (°) 99.664 (4) 113.043 (7)
V (Å3)1395.21 (9)1339.69 (13)
Z44
Radiation typeMo KαMo Kα
µ (mm−1)0.080.08
Crystal size (mm)0.29 × 0.25 × 0.210.32 × 0.28 × 0.23
Data collection
DiffractometerOxford Diffraction Xcalibur-S
diffractometer		Oxford Diffraction Xcalibur-S
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2006)		Multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.978, 0.9840.975, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections		9836, 2448, 1988 8644, 2356, 1625
Rint0.0200.036
(sin θ/λ)max (Å−1)0.5950.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.099, 1.06 0.059, 0.188, 1.10
No. of reflections24482356
No. of parameters172172
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.20, −0.150.10, −0.34

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

 

Acknowledgements

We are grateful to the DST for financial support. We also thank SAIF–Mumbai for recording the spectroscopic data. SV thanks IIT–Bombay and UGC–New Delhi for the award of a research fellowship. SK thanks the DST for the award of a J. C. Bose fellowship. SK thanks Mr Darshan Mhatre for his help in collecting the crystal data.

References

First citationBott, S. G., Marchand, A. P., Alihodzic, S. & Kumar, K. A. (1998). J. Chem. Crystallogr. 28, 251–258.  Web of Science CSD CrossRef CAS Google Scholar
 First citationFlippen-Anderson, J. L., George, C., Gilardi, R., Zajac, W. W., Walters, T. R., Marchand, A., Dave, P. R. & Arney, B. E. (1991). Acta Cryst. C47, 813–817.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationGroom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671.  Web of Science CrossRef CAS Google Scholar
 First citationKotha, S. & Dipak, M. K. (2006). Chem. Eur. J. 12, 4446–4450.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationKotha, S., Manivannan, E. & Sreenivasachary, N. (1999). J. Chem. Soc. Perkin Trans. 1, pp. 2845–2848.  Web of Science CrossRef Google Scholar
 First citationKotha, S., Seema, V., Singh, K. & Deodhar, K. D. (2010). Tetrahedron Lett. 51, 2301–2304.  Web of Science CrossRef CAS Google Scholar
 First citationKruger, H. G., Rademeyer, M. & Ramdhani, R. (2005). Acta Cryst. E61, o3968–o3970.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationLinden, A., Romański, J., Mlostoń, G. & Heimgartner, H. (2005). Acta Cryst. C61, o221–o226.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationMarchand, A. P. (1989a). Chem. Rev. 89, 997–1010.  CrossRef Web of Science Google Scholar
 First citationMarchand, A. P. (1989b). Chem. Rev. 89, 1011–1033.  CrossRef CAS Web of Science Google Scholar
 First citationMehta, G. & Srikrishna, A. (1997). Chem. Rev. 97, 671–720.  CrossRef PubMed CAS Web of Science Google Scholar
 First citationOlah, G. (1990). Cage Hydrocarbons. New York: Wiley.  Google Scholar
 First citationOsawa, E. & Yonemitsu, O. (1992). Carbocyclic Caged Compounds. New York: VCH.  Google Scholar
 First citationOxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationVon, I., Hargittai, I. & Hargittai, M. (1986). Symmetry Through the Eyes of a Chemist. New York: Wiley.  Google Scholar
 First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
Volume 70| Part 11| November 2014| Pages 410-414
doi:10.1107/S1600536814023149
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